Electrode structure for solid state electrochemical devices

ABSTRACT

A composite oxygen electrode/electrolyte structure for a solid state electrochemical device having a porous composite electrode in contact with a dense electrolyte membrane, which electrode includes: (a) a porous structure having interpenetrating networks of an ionically-conductive material and an electronically-conductive material; and (b) an electrocatalyst different from the electronically-conductive material, dispersed within the pores of the porous structure. This electrode structure is relatively simple to manufacture, requiring relatively few steps to infiltrate an electrocatalyst precursor material to obtain an electrode structure which will perform advantageously in a solid oxide fuel cell, has a relatively low internal resistance, and permits the selection of an optimal electronically-conductive material and electrocatalyst.

BACKGROUND OF THE INVENTION

This invention relates to solid state electrochemical devices comprisedof one or more electrodes in contact with a solid state electrolytemembrane. More specifically, this invention relates to solid stateelectrochemical devices in which a lower total internal resistance ofthe cell results in better performance of the device, such as solidoxide or ceramic fuel cell devices or solid oxide or ceramicelectrolytic cells.

A solid state electrochemical cell comprises two electrodes, the anodeand the cathode, and a dense solid electrolyte membrane which separatesthe anode and cathode regions of the cell. The anodic and cathodicreactions occur at the anode/electrolyte and cathode/electrolyteinterfaces, respectively. The solid electrolyte membrane is a materialcapable of conducting ionic species, such as oxygen ions, sodium ions,fluoride ions, or hydrogen ions, yet has a low electrical conductivity.The electrolyte membrane must be impermeable to the electrochemicalreactants.

It is known to prepare a solid oxide fuel cell comprising a denseelectrolyte membrane of a ceramic oxygen ion conductor, a porous anodelayer of a ceramic or a metal or, most commonly, a ceramic-metalcomposite, in contact with the electrolyte membrane on the fuel side ofthe cell, and a porous cathode layer of an electronically-conductivemetal oxide on the oxidant side of the cell, which generates electricitythrough the electrochemical reaction between a fuel and an oxidant. Thisnet electrochemical reaction involves charge transfer steps that occurat the interface between the ionically-conductive electrolyte membrane,the electronically-conductive electrode and the vapor phase (fuel oroxygen). The contribution of these charge transfer steps, in particularthe charge transfer occurring at the oxygen electrode, to the totalinternal resistance of a solid oxide fuel cell device can besignificant, especially if the fuel cell operating temperature isrelatively low. Reducing the internal resistance of a solid oxide fuelcell device improves its performance characteristics.

Electrode structures comprising a porous layer of electrolyte particleson a dense electrolyte membrane with electrocatalyst material on andwithin the porous layer of electrolyte are known. In such electrodes,the electrocatalyst material is continuous on the surface of the porouselectrolyte material to create a three phase boundary (TPB) where theelectrolyte material, electrocatalyst, and gas are in contact. Theelectrode is prepared by applying an electrocatalyst precursor materialas a slurry to a porous electrolyte structure, and then heating theprecursor material to form the electrocatalyst. However, it is usuallynecessary to repeat the process of applying the electrocatalystprecursor material to the porous substrate several times in order toprovide enough electrocatalyst to obtain a fuel cell with the desiredperformance characteristics. For fuel cell applications, this method ofcreating the layer of electrocatalyst in and on the porous electrolytestructure by repeated applications of the electrocatalyst slurry maycreate more process steps in the preparation of the fuel cell than wouldbe desirable in a commercial manufacturing process. In addition, theperformance characteristics of the electrode structure prepared by suchprocesses, such as the voltage at a certain current density, may be lessthan desirable for certain applications.

SUMMARY OF THE INVENTION

In one aspect, this invention is a composite oxygenelectrode/electrolyte structure for a solid state electrochemical devicehaving a porous composite electrode in contact with a dense electrolytemembrane, said electrode comprising:

(a) a porous structure having interpenetrating networks of anionically-conductive material and an electronically-conductive material;and

(b) an electrocatalyst different from the electronically-conductivematerial, dispersed within the pores of the porous structure.

In a second aspect, this invention is a process for preparing a layeredcomposite oxygen electrode/electrolyte structure having a porouscomposite electrode in contact with a dense electrolyte membrane whichcomprises the steps of:

(i) contacting a mixture comprising particles of an ionically-conductivematerial and an electronically-conductive material with a layercomprising an ionically-conductive electrolyte material to form anassembly comprising a layer of the mixture on at least one side of thelayer of the electrolyte material;

(ii) sintering the assembly; and

(iii) infiltrating the assembly with a solution or dispersion of anelectrocatalyst precursor.

It has been discovered that the electrode structure and process of theinvention provide an oxygen electrode/electrolyte assembly which isrelatively simple to manufacture, requiring relatively few steps toinfiltrate an electrocatalyst precursor material to obtain an electrodestructure which will perform advantageously in a solid oxide fuel cell,has a relatively low internal resistance, and which permits theselection of an optimal electronically-conductive material andelectrocatalyst. The invention also provides an electrode/electrolytestructure with an advantageous three phase boundary (TPB) length betweenthe electrocatalyst, the ionically-conductive material in contact withthe electrocatalyst, and the gas phase. When utilized as the cathode andelectrolyte membrane of a solid oxide fuel cell, such fuel cells haveadvantageous power densities at relatively low operating temperatures,such as about 700°-800° C. These and other advantages of the inventionwill be apparent from the description which follows.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1-5 illustrate the performance of anode/electrolyte/cathodestructures prepared and tested in accordance with the proceduresdescribed in Examples 1-5, respectively.

DETAILED DESCRIPTION OF THE INVENTION

The term "oxygen electrode" as used herein refers to the electrode atwhich oxygen is either reduced, or oxygen anions are oxidized, dependingon the function of the cell, such as the cathode portion of a solidoxide fuel cell or the anode portion of an electrolytic cell. The oxygenelectrode portion of the electrode/electrolyte structure of theinvention comprises a porous, solid-solid mixture ofionically-conductive material and electronically-conductive material,having an electrocatalyst different from the electronically-conductivematerial dispersed within its pores. The mixture comprises a continuousphase of the ionically-conductive material and a continuous phase of theelectronically-conductive material, which form interpenetrating networkswith respect to each other.

The electrode/electrolyte structure of the invention may be prepared byany suitable method. For example, the unsintered mixture ofelectronically-conductive and ionically-conductive materials may bedeposited on a layer comprising a sintered or unsinteredionically-conductive electrolyte material prior to being sintered, toensure sufficient contact between the layers, as illustrated in theprocess of the second aspect of the invention. In one embodiment of sucha process, the mixture of ionically-conductive andelectronically-conductive materials is deposited on an unsintered layerof electrolyte material and the mixture and electrolyte layer aresintered simultaneously. In another embodiment, the mixture is depositedon a previously sintered layer of electrolyte, and then sintered.

The mixture of ionically-conductive and electronically-conductiveparticles may be applied to the layer comprising particles of anelectrolyte material (hereafter "electrolyte layer"), by any suitablemeans such as, for example, tape casting methods, painting orsilk-screening a slurry of the material (s) onto the electrolyte layer,or by vapor deposition techniques such as plasma-spraying directly ontothe solid electrolyte structure. When sintered, the ionically-conductiveand electronically-conductive materials form interpentrating networkscomprised of fused grains of ionically-conductive material orelectronically-conductive material, respectively. After the mixture issintered to the electrolyte layer, an electrocatalyst is incorporatedinto the porous network of electronically-conductive particles andionically-conductive particles by any suitable technique, such as byinfiltrating the network with a solution or dispersion of anelectrocatalyst precursor and heating the infiltrated network underconditions sufficient to form the corresponding electrocatalyst.

The term "electronically-conductive material" as used herein means amaterial having an electronic conductivity of at least about 10⁻¹Siemens/cm (S/cm) at the operating temperature of the device.Preferably, the conductivity of the material is at least about 10 S/cm,more preferably at least about 100 S/cm. This phase must also becompatible with the electrolyte layer and the ionically-conductivematerial of the composite electrode. For example, it must notsignificantly undergo reactions with either the layer or the material atthe processing or operating temperatures to form a new phase withinsufficient conductivity or electrocatalytic properties for use in apractical device. The primary function of the electronically-conductivematerial is the transport of electricity (electrons) either from theexternal circuit to the active sites of the electrode or from the activesites to the external circuit, although the electronically-conductivephase may also have a significant ionic conductivity and may also be agood electrocatalyst.

The term "electrocatalyst" as used herein refers to a material withsufficient catalytic activity for the electrochemical reaction(s)occurring at the electrode for its use in a practical device. Thismaterial must also be compatible with the electrolyte layer, theionically-conductive material and the electronically-conductivematerial, at the operating temperature of the device. The primaryfunction of this material is to efficiently promote the desiredelectrochemical reaction(s) within the electrode.

Suitable electronically-conductive materials and electrocatalystsinclude metallic or semi-conductive materials such as metals, conductivemetal alloys, conductive metal oxides, and mixtures thereof. Examples ofsuitable metals include platinum, silver, palladium, rhodium, iridiumand ruthenium. Examples of suitable conductive metal alloys includeconductive metal oxides such as the rare earth perovskites having thegeneral formula: A_(1-a) A'_(a) B_(1-b) B'_(b) O₃₋δ, where 0≦a≦1; 0≦b≦1;-0.2≦δ≦0.5; A is at least one rare earth cation such as La, Pt, Nd, Smor Tb; A' is at least one dopant cation, such as the alkaline earthcations Sr or Ca; B is at least one transition element cation selectedfrom the group consisting of Mn, Co, Fe, Cr, or Ni; and B' is atransition element cation different from B. Examples of such conductiverare earth perovskites include La_(1-a) Sr_(a) MnO₃₋δ ("LSM"), where0≦a≦0.5; Pr_(1-a) Sr_(a) MnO₃₋δ ("PSM") where 0≦a≦0.6; Pr_(1-a) Sr_(a)CoO₃₋δ, where 0≦a≦0.5; La_(1-a) Sr_(a) Co_(1-b) Fe_(b) O₃₋δ, where0≦a≦0.4 and 0≦b≦0.8; La_(1-a) Sr_(a) Co_(1-b) Ni_(b) O₃₋δ, where 0≦a≦0.6and 0≦b≦0.4 and La_(1-a) Sr_(a) CrO₃₋δ or La_(1-a) Ca_(a) CrO₃₋δ where0≦a≦0.5. Examples of other conductive metal oxides include the productsformed from mixtures of In₂ O₃ --PrO₁.83 --ZrO₂, having compositionratios of In₂ O₃ of 0 to 90%, PRO₁.83 of 10 to 100%, ZrO₂ of 0 to 50%and the products formed from mixtures of Co₃ O₄ --PrO₁.83 --ZrO₂, havingcomposition ratios of Co₃ O₄ of 0 to 70%, PRO₁.83 of 30 to 100% and ZrO₂of 0 to 50%. Other conductive or semi-conductive materials having aconductivity of at least 0.1 S/cm at the cell operating temperature mayalso be useful. Preferably, the electronically-conductive material israre earth manganite such as PSM or LSM, particularly when theelectrolyte material is a doped zirconia.

The term "ionically-conductive material" as used herein means a materialwith sufficient ionic conductivity for its use in a practical fuel celldevice (typically σ_(i) ≧10⁻³ S/cm at the operating temperature of thedevice). This material must also be compatible with theionically-conductive and electronically-conductive materials to which itis adjacent in the electrolyte/electrode structure. For example, it mustnot significantly undergo reactions with either of those materials atthe processing or operating temperatures to form a new phase withinsufficient conductivity or electrocatalytic properties for use in afuel cell. The primary function of the ionically-conductive material inthe electrode is the efficient transport of ions from the active sitesof the electrode to the electrolyte membrane, and vice verse, dependingon whether the device in which the electrode is utilized is a fuel cellor eletrolytic cell. However, the ionically-conductive material may alsohave a significant electronic conductivity and may also be a goodelectrocatalyst.

Suitable ionically-conductive materials include doped zirconias such asyttria-stabilized zirconia ("YSZ"), ytterbium-stabilized zirconia("YbSZ"), scandium-doped zirconia, ceria, gadolinium-doped ceria, Gd₀.19Pr₀.01 Ce₀.8 O_(2-y) (y varying with the oxidation states of the Gd andPt), strontium-doped BaCeO₃, rare earth- or alkaline earth-dopedLaAGaO₃, calcium-doped Gd₂ Ti₂ O₇, reaction products of mixtures ofPrCoO₃ -YSZ having the composition ratios of PrCoO₃ of 0 to 70%, YSZ of30 to 100% and mixtures thereof. Preferably, the ionically-conductivematerial is a doped zirconia, and is most preferably YSZ.

The electronically- and ionically-conductive materials are employed inamounts sufficient to form conductive networks among like particlesafter sintering, but are preferably present in an amount, based on thesolid volume of the materials used to prepare the porous layer, of atleast about 20 percent by volume of each and preferably no more thanabout 80 percent by volume of either. The size of the particles ofionically-conductive and electronically-conductive materials, as well asthe size of the grains of materials present after sintering (as may beobserved by Scanning Electron Microscopy) is preferably in the range offrom about 0.1-20 microns. The mixture used to prepare the porousinterpenetrating network may optionally contain a fugitive binder suchas an organic polymer, and/or a fugitive pore former such as carbonparticles, which will burn at or below the sintering temperature toincrease the porosity of the structure. Examples of suitable fugitivebinders include acrylates, poly(vinyl butyral), (available from Monsantoas Butvar™), polyvinyl acetone, methylcellulose, and styrene/butadienecopolymers.

The term "electrolyte membrane" as used herein refers to anionically-conductive solid membrane having an ionic conductivity (σ_(i))of at least about 10⁻³ S/cm at the operating temperature of the deviceand sufficiently low electronic conductivity (σ_(e)) for its use as theelectrolyte membrane which separates the anode from the cathode in asolid state electrochemical device. Preferably, σ_(e) /σ_(i) ≦10⁻², andmore preferably σ_(e) /σ_(i) ≦10³¹ 3. Preferably, the area-specificresistance of the membrane is less than about 0.1 Ω·cm², which may becalculated by dividing its thickness by its conductivity, σ. Theelectrolyte membrane may be prepared by any suitable method, such as bydepositing a slurry of an ionically-conductive electrolyte materialdirectly onto one of the electrodes, or by preparing a cast tape of anionically-conductive electrolyte material, which is laminated to a casttape of electrode material. In the most preferred embodiment, theionically-conductive electrolyte material is deposited onto a layer ofunsintered material, which, after sintering, will become the electrodeon the opposite side of the electrolyte membrane with respect to theelectrode prepared by the process of the invention. Either or both theanode or cathode side of a cathode/electrolyte membrane/anode structuremay be the electrode of the invention or prepared by the process of theinvention.

The assembly is then sintered under suitable pressure and temperatureconditions. The sintering conditions should be selected so that they aresufficient to fuse the majority of the like particles in the assemblylayer containing the ionically-conductive and electronically-conductiveparticles, as well as to fuse the majority of like particles at theelectrolyte membrane/electrode interface sufficiently to form anionically-conductive pathway therebetween. If the layer ofionically-conductive material has not been previously sintered, thesintering conditions should be selected to densify theionically-conductive material sufficiently to form a gas-impermeableelectrolyte membrane. Fugitive pore-forming materials which will burn ator below the sintering temperature may also be incorporated into themixture to control the porosity of the electrode layer, as discussedabove. The sintering conditions necessary to form the structure havingan optimum porosity (as far as the performance of the fuel cell orelectrolytic cell is concerned) may be readily determinedexperimentally.

In the preparation of the electrode/electrolyte structure of theinvention, after the mixture of ionically-conductive andelectronically-conductive materials has been sintered, the porousstructure or assembly formed from the mixture of theelectronically-conductive material and the ionically-conductive materialis then infiltrated with a solution or dispersion of an electrocatalystprecursor material. Preferably, a solution of a precursor material isutilized. Any electrocatalyst that can be formed by heat treating asolution precursor or the residue of evaporation of a solution precursorcan be utilized in the porous electrode structure by infiltrating theelectrode with the solution precursor, and then heating theelectrode/electrolyte assembly. Preferably, the electrocatalyst isPrCoO₃ or PrCoO₃ /silver, the reaction products formed from mixtures ofPrCoO₃ -YSZ with composition ratios of PrCoO₃ of 30 to 100%, YSZ of 0 to70%, La(Sr)CoO₃, or La(Sr)Co(Ni)O₃. If the ionically-conductive materialis YSZ or YbSZ, the electrocatalyst is preferably PrCoO₃. If theion-conducting material is ceria or a doped ceria, the electrocatalystis preferably La(Sr)CoO₃, La(Sr)Co(Ni)O₃, or La(Sr)Fe(Co)O₃.

Solution precursors of electrocatalysts include aqueous or non-aqueoussolutions of metal salts recited above, such as nitrates, acetates andcitrates. Furthermore, any electrocatalyst that can be formed bydeposition from or decomposition of a gas phase precursor can also beintroduced within the porous electrode structure by infiltrating theelectrode with said gas phase precursor. For example, La_(1-x) Sr_(x)MnO₃ may be formed within the porous structure by heating the structureafter it has been infiltrated with a solution containing a mixture of1-x molar equivalents of lanthanum nitrate, x molar equivalents ofstrontium nitrate, and 1 molar equivalent of manganese nitrate.

The porous structure may be infiltrated by any suitable means such as bypainting or silk screening the solution of the electrocatalyst materialinto the porous structure. If desired, a stack of cells may be assembledprior to being infiltrated and infiltrated simultaneously. If precursormaterials are used, the step of heating the material to form theelectrocatalyst is preferably carried out when the fuel cell is heatedto its operating temperature. The step of heating the electrocatalystprecursor to form the electrocatalyst may be carried out on the assemblyafter infiltration, or after the assembly has been used in thepreparation of a multi-cell stack.

The materials used to prepare the electronically- andionically-conductive phases of the composite electrode are preferablychosen to be compatible with the electrolyte membrane, so that reactionssignificantly deleterious to the performance of the cell do not occur atsintering or cell operating conditions. However, the catalyticproperties of the optimum electronically-conductive materials may beless than desirable. Since the electrocatalyst precursor is infiltratedafter the porous network layer and electrolyte layer are sintered, itneed only be compatible with the network and electrolyte layer attemperatures at which the precursor material is heated, or the fuel cellis operated, which are typically much lower than the temperature atwhich the electrode will have previously been sintered. Theelectronically-conductive material preferably has electronicconductivity, chemical compatibility with the electrolyte membrane atthe sintering, and fuel cell operating temperatures, both in terms ofchemical reactivity and coefficients of thermal expansion.

The porosity of the composite electrode structure containing theelectrocatalyst is preferably at least about 10 percent, more preferablyat least about 20 percent; but is preferably no greater than about 50percent, more preferably no greater than about 35 percent. The averagepore size of the composite structure is preferably at least about 0.1micron, more preferably at least about 1 micron; but is preferably nogreater than about 20 microns, more preferably no greater than about 10microns. If the structure is heated to form the correct form ofelectrocatalyst, it is preferably heated at a temperature below thesintering temperature of the materials and the porous layer so that theparticles do not further coarsen. The thickness of the sinteredelectrolyte membrane is preferably at least about 5 μm, more preferablyat least about 10 μm; but is preferably no greater than about 35 μm,more preferably no greater than about 20 μm. The thickness of thesintered composite electrode is preferably at least about 5 μm, morepreferably at least about 50 μm; but is preferably no greater than about500 μm, more preferably no greater than about 200 μm.

Solid oxide fuel cells which incorporate the electrode of the inventionpreferably have a peak power density of at least about 0.3 watt/cm²operating at 800° C. using hydrogen gas as a fuel and air as an oxidant.

Illustrative Embodiments

The following examples are given to illustrate the invention and shouldnot be interpreted as limiting it in any way. Unless stated otherwise,all parts and percentages are given by weight.

EXAMPLE 1

The anode portion of an anode/electrolyte/cathode structure is formed bypressing a 1.25" dia. disk from 2.5 g of a mixture of NiO(62 wt%)/YSZ(38 wt %). The mixture of NiO/YSZ is prepared by ball milling 31.0g of NiO (available from Johnson Matthey, Ward Hill, Mass.), 19.0 g ofYSZ (Tosoh TZ-8Y (available from Tosoh Ceramics, Boundbrook, N.J.) and1.45 g of a styrene/butadiene latex binder in 65 mL of ethanol and 10 mLof water for 1.5 days. A thin coating of YSZ (the ionically-conductiveelectrolyte material) is applied to one face of the NiO/YSZ disk byplacing 7 to 8 drops of a dispersion of YSZ in absolute ethanol on theface of the disk and quickly tilting the disk in a circular fashion tocompletely and as uniformly as possible cover the face of the disk. Thedispersion is prepared by sonicating a suspension of 0.5 g of YSZ in 20mL of absolute ethanol for about 4 minutes. The coated disk is allowedto dry for 50 minutes under a glass cover dish. The coating procedure isrepeated three more times for a total of four applications (thistypically yields a sintered YSZ electrolyte membrane about 15 μm thick).

A coating of a mixture of YSZ (ion-conductive material), LSM(electronically-conductive material), and graphite (fugitivepore-forming material) is applied to the face of the disk which waspreviously coated with YSZ. The YSZ/LSM/graphite mixture is prepared bysonicating for 4 minutes a suspension of 1.8 g YSZ (Tosoh TZ-8Y), 1.4 gLSM (La₀.8 Sr₀.2 MnO₃, Seattle Specialty Ceramics, Seattle, Wash.) and1.5 g of graphite (325 mesh size, available from Johnson Matthey) in 22mL of absolute ethanol. After drying for about 2 hours, the disk isfired to burn out the fugitive pore formers and binder and sinter thestructure, according to the following schedule: heat room temperature to300° C. in 1:10 (1 hour 10 minutes), 300° to 750° C. in 5:00, 750° to800° C. in 1:30, 800° to 1200° C. in 2:30, 1200° to 1225° C. in 3:00,cool 1225° to 1000° C. in 200°, 1000° to 500° C. in 2:30, then furnacecool from 500° C. to room temperature (RT). After firing, the disk isabout 1.0" dia. and is slightly warped. The disk is creep flattened byflat firing under the weight of a setter for 3 hours at 1250° C.

After cooling, the porous LSM/YSZ layer is infiltrated with an aqueoussolution of 1M praseodymium nitrate and 1M cobalt nitrate by applyingthe solution with a brush until the porous LSM/YSZ layer has fullyabsorbed the solution. After drying at room temperature for about 1hour, the disk is fired at 900° C. for 1 hour (the electrocatalystprecursor). After cooling, a second coating of Pt ink is applied to theanode face, a second infiltration of the cathode layer is performed,this time with an aqueous solution containing 1M praseodymium nitrate,1M cobalt nitrate, and 1M silver nitrate. After drying at about 110° C.for 1 hour, Pt ink is painted on the cathode face and silver mesh isattached to both the anode and cathode faces of the fuel cell, tofunction as current collectors. The cell assembly is then fired for 2hours at 875° C. The Pt ink and the silver mesh serve as currentcollectors for the cell testing apparatus.

The current-voltage response of the fuel cell is measured at 800° C.using humidified hydrogen (about 3% water) as the fuel gas and air asthe oxidant gas. The air flow across the cathode is maintained at about500 mL/minute and the fuel flow across the anode maintained at about 150mL/minute. The current-voltage data shown in FIG. 1 is collected with aHewlett-Packard DC Electronic Load in constant voltage mode after thecell has been operating for about 22.5 hours under a load of about 0.6ohm (V_(cell) =0.795 V, I_(cell) ˜1.3 A). A cell area of 2.34 cm² (thearea of a disk 0.68" dia.) is used to calculate the cell current densityand power density shown in FIG. 1. The slope of the plot of cell voltagevs. current density is the area specific resistance of the cell (0.35ohm-cm² from FIG. 1).

EXAMPLE 2

An anode/electrolyte/cathode structure is prepared as described inExample 1, except that the cell is heated to 800° C. for 12 hours, andcooled again to ambient temperatures prior to being infiltrated a singletime with the catalyst precursor to PrCoO₃. The cell is then tested inaccordance with the procedure described in Example 1, and the cell'scurrent-voltage data is shown in FIG. 2.

EXAMPLE 3

A 1.25" dia. disk is pressed from 2.5 g of a mixture containing 62 wt %of NiO (Alfa), 26 wt % of YSZ (Tosoh TZ-8Y), and 12 wt % of YbSZ (8 mol% Yb-doped ZrO₂, Seattle Specialty Chemicals). A thin coating of YbSZ isapplied to one face of the NiO/YSZ/YbSZ disk by placing 6 to 8 drops ofa dispersion of 8 mol % Yb-doped ZrO₂ in absolute ethanol on the face ofthe disk and quickly tilting the disk in a circular fashion tocompletely and as uniformly as possible cover the face of the disk. Thecoated disk is allowed to dry for 50 minutes under a glass cover dish.The coating procedure is repeated 4 more times for a total of 5applications. Next, a coating of a mixture of YbSZ, LSM, and graphite isapplied to the face of the disk previously coated with YbSZ by applyinga slurry containing 38 wt % YbSZ, 30 wt % LSM (La₀.8 Sr₀.2 MnO₃, SeattleSpecialty Ceramics) and 32 wt % graphite powder (available from JohnsonMatthey) in absolute ethanol. After drying, the disk is fired accordingto the following schedule: heat from room temperature to 300° C. in1:10, 300° to 750° C. in 5:00, 750° to 850° C. in 1:30, 850° to 1225° C.in 3:00, 1225° to 1250° C. in 3:00, 1250° to 1000° C. in 2:00, 1000° to500° C. in 1:30, 500° C. to room temperature in 0:50. After firing, thefuel cell is creep flattened under the weight of a setter for 3:00 at1250° C.

The YbSZ/LSM cathode of the fuel cell is then infiltrated with a 1Msolution of Pr and Co nitrates in water and heat treated for 1 hour at900° C. The infiltration/heat treatment procedure is repeated twice.After applying the platinum ink/silver mesh current collectors, the cellperformance is measured at 800° C. using humidified hydrogen as the fuelgas and air as the oxidant gas. The air flow across the cathode ismaintained at about 520 mL/minute and the fuel flow across the anodemaintained at about 150 mL/minute. The current-voltage response of thefuel cell is shown in FIG. 3. The cell produces a peak power of 0.95W/cm². The slope of the plot of cell voltage vs. current density gives avalue for the area specific resistance (ASR) of the cell of ASR=0.24Ω-cm².

EXAMPLE 4

Anode/electrolyte/cathode tapes of YSZ (Tosoh TZ-8Y), NiO/YSZ(NiO/YSZ=50/50 by weight), and LSM/YSZ/graphite (LSM/YSZ/C=100/30/20 byweight) are cast on a batch caster. The tape casting slips employ a50/50 mixture of methyl ethyl ketone/ethanol as the solvent, polyvinylbutyral (Monsanto) as the binder and dibutyl phthalate (Aldrich) as theplasticizer. The YSZ electrolyte layer tape is cast with a thickness of0.002", the NiO/YSZ anode layer tape is cast with a thickness of 0.010",and the LSZ/YSZ/graphite cathode layer tape is cast with a thickness of0.010". A layered structure consisting of LSM/YSZ/graphite cathode; (1layer)/YSZ electrolyte; (1 layer)/NiO/YSZ/anode; (5 layers) is producedby laminating the tapes at 70° C., 2 ksi isostatic pressure for 10minutes using an isostatic laminator. The layered structure is thencosintered according to the following schedule: 5° C./minute from RT to300° C.; 2° C./minute from 300° to 900° C.; hold at 900° C. for 1 hour;2.5° C./minute from 900° C. to 1250° C.; hold at 1250° C. for 3 hours;cool to RT at 5° C./minute.

The YSZ/LSM cathode of the fuel cell is infiltrated once with a 1Msolution of Pr and Co nitrates (electrocatalyst precursor) in water andheat treated for 1 hour at 900° C. After applying the platinumink/silver mesh current collectors, the cell performance is measured at800° C. using humidified hydrogen as the fuel gas and air as the oxidantgas. The air flow across the cathode is maintained at about 750mL/minute and the fuel flow across the anode maintained at about 200mL/minute. The current-voltage response of the fuel cell is shown inFIG. 4. The cell produces a peak power of 0.74 W/cm². The slope of theplot of cell voltage vs. current density gives a value for the areaspecific resistance of the cell of 0.33 Ω-cm².

EXAMPLE 5

A 1.25" dia. disk is pressed from 2.5 g of a mixture containing 62 wt %of NiO (Alfa), 26 wt % of YSZ (Tosoh TZ-8Y), and 12 wt % YbSZ (8 mol %Yb-doped ZrO₂, Seattle Specialty Ceramics). This mixture is prepared bythe same method described in Example 3 except no latex binder isemployed. A thin coating of YSZ is applied to one face of theNiO/YSZ/YbSZ disk by placing 6 to 8 drops of a dispersion of YSZ (TosohTZ-8Y) in absolute ethanol on the face of the disk and quickly tiltingthe disk in a circular fashion to completely and as uniformly aspossible cover the face of the disk. The dispersion is prepared bysonicating 0.497 g of YSZ in 20 mL of absolute ethanol for 2 minutes at100 W. The coating procedure is repeated two more times for a total ofthree applications. Next, two coatings of YbSZ are applied on top of theYSZ layer in the same manner. The YbSZ dispersion is prepared bysonicating 0.506 g of 8 mol % Yb-doped ZrO₂ (Seattle Specialty Ceramics)in 20 mL of absolute ethanol for 4 minutes at 100 W. Finally, a coatingof YbSZ/graphite is applied to the face of the disk previously coatedwith YbSZ by applying a slurry containing 38 wt % YbSZ, 30 wt % LSM, and32 wt % graphite powder (Alfa, -325 mesh) in absolute ethanol.

After drying, the disk is fired according to the following schedule:heat from room temperature to 300° C. in 1:10, 300° to 750° C. in 5:00,750° to 850° C. in 1:30, 850° to 1225° C. in 3:00, 1225° to 1250° C. in3:00, 1250° to 1000° C. in 2:00, 1000° to 500° C. in 1:30, 500° C. toroom temperature in 0:50. After sintering, the fuel cell is creepflattened under the weight of a setter according to the following firingschedule: heat from room temperature to 300° C. in 1:10, 300° to 750° C.in 5:00, 750° to 800° C. in 1:30, 800° to 1225° C. in 3:00, 1250° to1250° C. in 3:00, cool 1250° to 1000° C. in 2:00 and 1000° to 500° C. in1:30, then furnace cool from 500° C. to room temperature. Aftersintering, the cells are about 1.0" dia. and are slightly warped. Thewarp is removed by creep flattening the cells under the weight of asetter for 3 hours at 1250° C.

The LSM/YbSZ layer is infiltrated once with the 1M PrCoO₃ -silverprecursor and the anode and cathode faces are painted with Pt ink. Thecell is then fired at 900° C. for 1 hour. After cooling, theinfiltration is repeated and the anode and cathode faces again paintedwith Pt ink and fired for 1 hour at 900° C. Another coating of Pt ink isapplied to the cathode face and the cell fired a third time for 1 hourat 900° C. Finally, another application of Pt ink is made to the anodeand cathode faces, and the cell sandwiched between silver mesh and firedat 900° C. for 1 hour under the weight of two setters. Mica sheets areplaced between the cell assembly and the setters to prevent the cellfrom sticking to the setters. Any mica stuck to the cell after firing isremoved with light sanding. The cell is placed in a test stand andtested under the conditions noted in FIG. 5. The current-voltageresponse of the fuel cell is shown in FIG. 5.

What is claimed is:
 1. A composite oxygen electrode/electrolytestructure for a solid state electrochemical device having a porouscomposite electrode in contact with a dense electrolyte membrane, saidelectrode comprising:(a) a porous structure having interpenetratingnetworks of an ionically-conductive material and anelectronically-conductive material; and (b) an electrocatalyst differentfrom the electronically-conductive material, dispersed within the poresof the porous structure.
 2. The structure of claim 1 wherein theionically-conductive material comprises yttria-stabilized zirconia, andthe electronically-conductive material is La_(1-a) SR_(a) MnO₃₋δ,Pr_(1-b) Sr_(b) MnO₃₋δ, or mixture thereof, where 0≦a≦0.5, 0≦b≦0.6 and0.2≦δ0.5.
 3. The structure of claim 1 wherein the ionically-conductivematerial comprises ytterbium-stabilized zirconia, and theelectronically-conductive material is La_(1-a) Sr_(a) MnO₃₋δ, Pr_(1-b)Sr_(b) MnO₃₋δ, or a mixture thereof, where 0≦a≦0.5, 0≦b≦0.6 and0.2≦δ≦0.5.
 4. The structure of claim 1 wherein the electrolyte membranecomprises yttria-stabilized zirconia and has a thickness of at leastabout 0.5 μm and no greater than about 30 μm and the electrode has athickness of at least about 10 μm and no greater than about 200 μm. 5.The structure of claim 1 wherein the electrolyte membrane comprisesytterbium-stabilized zirconia and has a thickness of at least about 0.5μm and no greater than about 30 μm and the electrode has a thickness ofat least about 10 μm and no greater than about 200 μm.
 6. The structureof claim 4 wherein the ionically-conductive material comprisesytterbium-stabilized zirconia, and the electronically-conductivematerial is La_(1-a) Sr_(a) MnO₃₋δ, Pr_(1-b) Sr_(b) MnO₃₋δ, or mixturethereof, where 0≦a≦0.5, 0≦b≦0.6 and 0.2≦δ≦0.5.
 7. The structure of claim4 wherein the ionically-conductive material comprises yttria-stabilizedzirconia and the electronically-conductive material is La_(1-a) Sr_(a)MnO₃₋δ, Pr_(1-b) MnO₃₋δ, or a mixture thereof, where 0≦a≦0.5, 0≦b≦0.6and 0.2≦δ≦0.5.
 8. The structure of claim 1 wherein theionically-conductive material comprises ceria or doped ceria, and theelectronically-conductive material is La_(1-a) Sr_(a) MnO₃₋δ, Pr_(1-b)MnO₃ -δ, or a mixture thereof, where 0≦a≦0.5, 0≦b≦0.6 and 0.2≦δ≦0.5. 9.The structure of claim 1 wherein the electrocatalyst comprises PrCoO₃.